DE3106186A1 - METHOD FOR PRODUCING ORGANOPOLYSILOXANS AND USE OF THIS ORGANOP - Google Patents

Description

Process for the preparation of organopolysiloxanes and the use of these organopolysiloxanes " _t _

From DE-OS 28.23 118 (published November 29, 1979, Wacker-Chemie GmbH) is already a process for the production of SiC-gebuhdene Organopolysiloxane resins containing vinyl groups, that is to say SiC-bonded organofunctional groups, are known. In contrast For this known method, the method according to the invention can also be used outside the narrow temperature range of 90 ° + 5 ° C and not only with organofunctional organosiloxanes but also with organofunctional organosilanes will. · ■

The invention relates to a process for the preparation of organopolysiloxanes with SiC-bonded organofunctional groups by reacting Si-bonded hydroxyl and / or alkoxy groups and an average of 0.85 to 1.8 monovalent, SiC-bonded, optionally halogenated hydrocarbon radicals per Si atom containing organopolysiloxane with organosilicon compound which has alkoxy groups and / or siloxane oxygen and at least one SiC-bonded organofunctional radical per molecule, characterized in that the reaction is carried out in an organic solvent
in the presence of a basic catalyst
is carried out.

The organopolysiloxanes used in the process according to the invention with Si-bonded hydroxyl or alkoxy groups and an average of 0.85 to 1.8 monovalent, SiC-bonded

those, optionally halogenated hydrocarbon radicals per Si atom are preferably those composed of units of the general formula

In this formula, E means the same or different, monovalent, optionally halogenated hydrocarbon radicals, R hydrogen or identical or different, monovalent * Alkyl radicals, χ and y are each O, 1, 2 or 3 with the proviso that χ has an average value of 0.85 to 1.8, y has an average value of 0.01 to 0.4 and at for each individual unit the sum of χ + y at most 3 is.

Examples of hydrocarbon radicals R are alkyl radicals with 1 to 18 carbon atoms, such as the methyl, ethyl, n-propyl, isopropyl and 2-ethylhexyl radicals and also hexyl and octadecyl radicals; Alkenyl radicals having 2 to 5 carbon atoms, such as vinyl, allyl, ethylallyl and butadienyl radicals; Cycloalkyl radicals, such as the cyclphexyl radical; Aryl radicals, such as the phenyl radical; Alkaryl residues with 7 up to 16 carbon atoms, such as tolyl radicals; and alkaryl radicals having 7 to 16 carbon atoms, such as the beta-phenylethyl radical.

Examples of halogenated hydrocarbon _{radicals R are the 3 i} 3 »3-trifluoropropyl radical and chlorobenzene radicals.

Preferably at least 20 % of the number of radicals R consists of phenyl radicals or of 5 to 18 carbon atoms having alkyl radicals.

Examples of alkyl radicals R are methyl, ethyl, n-propyl and isopropyl radical.

The organopolysiloxanes used in the process according to the invention preferably contain Si-bonded hydroxyl and / or alkoxy groups and an average of 0.85 to 1.8 monovalent ", SiC-bonded, optionally halogenated hydrocarbon residues per Si atom on average 10 to 1,000 Si atoms per molecule and an average of at least 2 sig-bonded people Hydroxyl and / or alkoxy groups per molecule.

As an organopolysiloxane with Si-bonded hydroxyl and / or alkoxy groups as much as an average of 0.85 to 1.8 monovalent, SiC-bonded, optionally halogenated hydrocarbon radicals one type of organopolysiloxane or a mixture can be used per Si atom from at least two different types of organopolysiloxanes can be used, as long as Si-bonded in this mixture Hydroxyl and / or alkoxy groups and an average of 0.85 to 1.8 monovalent, SiC-bonded, optionally halogenated Hydrocarbon residues are present per Si atom.

As organosilicon compounds, the alkoxy groups and / or Si-1-oxane oxygen , · So oxygen in the group = SiOSi =, and at least one SiC-bonded organofunctional per molecule Have the remainder are trialkoxysilanes of the general formula

R ^ Si

where R is the organofunctional radical and R- ^ are the same or different Alkyl groups denote the partial hydrolysates of such silanes and linear ones having 2 to 20 Si atoms per molecule or cyclic organo (poly) siloxanes from units of the general formula

^E a ^Si0 3-a>

in which E and R each have the meaning given above and a is 1 or 2, preferably with 2 to 9 S atoms per molecule.

It can be one kind of such organosilicon compounds with organofunctional Remainder or a mixture of at least two types of such organosilicon compounds can be used.

Examples of organo (poly) siloxanes of those indicated above Kind are those of the formulas

* (R ² E ₂ Si) ₂ O,

(E ² E ₂ SiOSiRR ² ) ₂ 0 and
(E ² ESiO) ₃ .

Λ
The examples for alkyl groups E also apply in full

• z
for the alkyl groups E.

2 Examples of organofunctional bests R are those of the! "Or- ·

CH ₂ = CH -

CH ₂ »C (CH ₅ ) COO (CH ₂ ) HS (CH ₂ ) ₃ -

(CH ₂ ) ₂ NH (CH ₂ ) ₅ -

CH ₂ - CHCH ₂ O (CH ₂ ) ₃ °

(CH ₂ )

HO (CH ₂ ) ₃
Cl (CH ₂ ) ₃

Individual examples of silanes or organo (poly) siloxanes with

organofunctional Eest R are

beta-aminoethyl-gamma-aminopropyltrimethoxysilane gamma-methacryloxyprbpyltrimethoxysilane and sym.-Di-gajma-hydroxypropyltetramethyldisiloxane and 1-gamma-hydroxypropyl-i, 1,3 »3» 3-pentamethyldisiloxane.

The ratio of the amount of organosilicon compound that Alkoxy groups and / or siloxane oxygen and at least per molecule has a SiC-bonded organofunctional radical, the amount of Si-bonded hydroxyl and / or alkoxy groups and an average of 0.85 to 1.8 monovalent, SiC-bonded, optionally halogenated hydrocarbon radicals per organopolysiloxane containing Si atoms can be used within wide limits vary. In the process according to the invention, 1 to 30 percent by weight of organosilicon compound, the alkoxy groups and / or siloxane oxygen and per molecule has at least one SiC-bonded organofunctional radical, based on the total weight of the one according to the invention Process used organosilicon compounds used.

Organic solvents which can be used in the process according to the invention are all organic solvents in which all of the organosilicon compounds used in the process according to the invention are soluble at least at the respective reaction temperature and which are inert to the other constituents of the reaction mixture. Aromatic solvents such as benzene, toluene or xylenes and chlorobenzene are preferred. Further examples of suitable solvents are alkanes having boiling points in the range of 120 ° to 180 ⁰ C at 1 bar, or about 1 bar; Alcohols, esters, ketones or glycol ethers.

One kind of organic solvent or a mixture of at least two kinds of such solvents can be used.

Organic solvent is preferably used in amounts of 4Ό up to 70 percent by weight, based on the total weight of the mixture of organic solvent, basic catalyst and organosilicon compounds to be reacted with one another are used.

The basic catalysts used in the process according to the invention all basic catalysts are used with which the condensation of Si-bonded hydroxyl groups with Si-bonded alkoxy groups or the rearrangement of siloxane compounds, which is also referred to as "equilibration", was or could be promoted. Are particularly preferred Alkali metal carbonates and alkali metal hydroxides. Also preferred are alkali metal alcoholates and alkali metal oxyacylates, like potassium acetate. The alkali metal in these catalysts can be lithium, "" "sodium, potassium, rubidium, or cesium act, with sodium and potassium being preferred as alkali metals, in particular because of their easy accessibility. Further examples suitable catalysts are potassium methyl siliconate and basic quaternary ammonium compounds, such as those from tetramethylammonium hydroxide and tetramethylammonium siloxanolate made by octamethylcyclotetrasiloxane.

One type of basic catalyst or a mixture of at least two types of basic catalyst, e.g. B. a mixture made of sodium hydroxide and potassium ethylate, can be used.

The amount of basic catalyst can vary within wide limits. She can. z. B. 5 percent by weight, based on the total weight of the mixture of organic solvent, basic catalyst and organosilicon compounds to be reacted with one another. However, 10 to 1,000 parts by weight of basic catalyst per million parts by weight of the mixture are preferred of organic solvent, basic catalyst and organosilicon compounds to be reacted with one another.

The reaction is preferably carried out at the reflux temperature of the solvent and at the pressure of the surrounding atmosphere. If desired, however, higher or lower temperatures and / or higher or lower pressures can also be used will.

If the organosilicon compounds to be reacted with one another are free or practically free of Si-bonded alkoxy groups, the organopolysiloxanes with SiC-bonded organofunctional groups produced according to the invention contain at most 1 percent by weight Si-bonded hydroxyl groups.

If at least one of the organosilicon compounds to be reacted with one another Contains Si-bonded alkoxy groups, so contain the organopolysiloxanes prepared according to the invention at most 10 mol percent S-i bonded alkoxy groups, if at the condensation of Si-bonded hydroxyl groups. Enough water was released and / or water as such or e.g. in the form of salt hydrates, such as sodium carbonate decahydrate the reaction according to the invention was present or added to the product obtained and the E-Och thus obtained was basic Catalyst-containing mixture was heated.

With the SiC-bonded organofunctional ones produced according to the invention Organopolysiloxanes containing groups can be carried out in all reactions that have been carried out with those previously known organopolysiloxanes with organofunctional groups could be carried out. Thus, according to the invention produced, containing SiC-bonded organofunctional groups Organopolysiloxanes for the production of modified polymers by copolymerization with an aliphatic double bond containing monomer or reaction with further polymer be used.

Organopolysiloxanes prepared according to the invention which contain at least one SiC-bonded organic group with a methacryloxy radical can thus be used own, e.g. B. with acrylates, methacrylates,

Itaconic acid dimethyl ester, acrylic acid, ■ hydroxyethyl methacrylate, Yinylpyrrolidone or styrene or mixtures of at least two such monomers are copolymerized and give clear, hard copolymers, the excellent gas, in particular Oxygen permeability, so that these copolymers suitable as materials for contact lenses.

Organopolysiloxanes produced according to the invention which have at least one SiC-bonded organic group with an amino and / or imino group can ζ. B. be implemented with epoxy resins. Organopolysiloxanes prepared according to the invention with at least one ξ COH group can, for. B. be reacted with isocyanates. * '

example 1

To 900 g of a hydrolyzate of C ₆ H ₁ -SiCl ^ 5 percent by weight of Si-bonded hydroxyl groups, a melting point of 53 C and an average molecular weight of 1,500 g / mol in 900 g of toluene, 90 g of beta-aminoethyl-gamma-aminopropyltrimethyloxysilan and Given 0.5 g of anhydrous sodium carbonate. The mixture obtained in this way is heated to boiling under a flow of ice for 4 hours. Then the constituents boiling up to 150 ° C at 1 bar, including the water split off during the reaction, are distilled off and then filtered.

The beta-aminoethyl-gamma-aminopropyl groups thus obtained as Organopolysiloxane containing organofunctional groups has an average molecular weight of about 3260 g / mol and contains at most 0.5 percent by weight of Si-bonded hydroxyl groups. It is with the same parts by weight Epoxy resin based on 2,2-bis (4-hydroxyphenyl) propane mixed with an average molecular weight of about 350 g / mol. The mixture hardens at room temperature forming a clear, uniform film.

.; -;.; ...;. 3106i86

-40-

Example 2 '. '. .

90 g of gamma-methacryloxypropyltrimethoxysilane and 0.5 g of anhydrous sodium carbonate are added to 900 g of the hydrolyzate of CgH _{1 -SiCl ^ in 900 g of toluene, which is described in more detail in Example 1.} The mixture thus obtained is refluxed for 4 hours. It is then filtered and then the ^{constituents boiling up to 150 °} C. at 1 bar are distilled off.

The gamma-methacryloxypropyl groups thus obtained as organofunctional parts Organopolysilane containing groups melts at 123 ° C.

2 g of this resin are dissolved in 98 g of methyl methacrylate and 75 g of this resin in 25 g of methyl methacrylate. After addition of 0.1 g Dicyclohexylperoxyä-dicarbonate 120 minutes heated to 40 ⁰ C. Clear, hard copolymers are obtained in each case.

Example 3

To 240 g of the hydrolyzate described in more detail in Example 1 of CgHt-SiCl ^ and 360 g of one in each of the terminal units Si-bonded hydroxyl group-containing diorganopolysiloxane from 75 mol percent dimethylsiloxane units and 25 mol percent Vinylmethylsiloxane units with a viscosity of about

P Λ ·

100 mm s "in 900 g of toluene, 30 g of gamma-methacryloxypropyltrimethoxysilane and 0.5 g of anhydrous sodium carbonate added. The mixture thus obtained is heated for 8 hours to boiling under reflux. The mixture is then filtered, and thereafter, the I50 up to ⁰ C at 1 bar boiling components distilled off.

The gamma-methacryloxypropyl groups thus obtained as organofunctional Organopolysiloxane containing groups is clear and viscous.

Example 4

90 g of sym.-di-gamma-hydroxypropyltetramethyldi - siloxane and, 0.15 g of potassium hydroxide in 100 g of water the mixture is heated for 6 hours to boiling under reflux After cooling it is filtered up to 120 ⁰ C at approximately 16 mbar boiling substances are distilled off from the filtrate... According to the H-NMR spectrum, the liquid obtained in this way contains 15 percent by weight of SiC-bonded hydroxypropyl groups.

Example 5 " ^M

A 50 percent by weight solution of the organopolysiloxane containing gamma-methacryloxy groups as organofunctional groups in methyl methacrylate, prepared according to Example 5, is mixed with 2 percent by weight, based on its weight, of dicyclohexyl peroxydicarbonate, dried over anhydrous sodium sulfate, filtered, saturated with nitrogen and left at 15 ° C. for 16 hours calmly. The temperature of this composition is ^{then increased to 110 °} C. within 8 hours and then allowed to cool again. A hard, clear body is obtained.

Hard, clear bodies are also obtained in each case when the methyl methacrylate is replaced in the procedure described above is through

a mixture of methyl methacrylate and styrene or a mixture of methyl methacrylate and dimethyl itaconate or ν a mixture of methyl methacrylate and acrylic acid or "

a mixture of methyl methacrylate and hydroxyethyl methacrylate. %

Claims (4)

3106136 Fat claims 1. Process iur production of organopolysiloxanes with SiC-bonded organofunctional groups through conversion of Si-bonded hydroxyl and / or alkoxy groups as well as average 0.85 to 1.8 monovalent SiC-bonded, optionally halogenated hydrocarbon residues per Si atom on " pointing organopolysiloxane with organosilicon compound, the alkoxy groups and / or siloxane oxygen and per molecule has at least one SiC-bonded organofunctional Eest, characterized in that that implementation in organic solvent is carried out in the presence of a basic catalyst. 2. The method according to claim 1, characterized in that that alkali metal carbonate or alkali metal hydroxide is used as the basic catalyst. 3. Use of the organopolysiloxanes prepared according to claim 1 or 2 with SiC-bonded organofunctional groups for the production of modified polymers by copolymerization with monomer containing aliphatic double bond or reaction with further polymer. 4. Use of the organopolysiloxanes prepared according to claim 1 or 2, which have at least one SiC-bonded organic group with a methacryloxy radical, for copolymerization with acrylates, methacrylates, dimethyl itaconate, Acrylic acid, hydroxyethyl methacrylate, vinyl pyrrolidone or styrene or mixtures of at least two such monomers, including the manufacture of hard contact lenses for the human eye.